US20110136963A1 - Method for snythesizing amphiphilic gradient copolymers soluble in an alkaline medium - Google Patents

Method for snythesizing amphiphilic gradient copolymers soluble in an alkaline medium Download PDF

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US20110136963A1
US20110136963A1 US13/058,383 US200913058383A US2011136963A1 US 20110136963 A1 US20110136963 A1 US 20110136963A1 US 200913058383 A US200913058383 A US 200913058383A US 2011136963 A1 US2011136963 A1 US 2011136963A1
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styrene
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Laurence Couvreur
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Arkema France SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the preparation of amphiphilic copolymers by Controlled Radical Polymerization in the presence of a RAFT (Reversible Addition Fragmentation Transfer) agent.
  • the copolymers of the invention exhibit low polydispersity indices and low viscosities in solution and are readily soluble in an alkaline medium.
  • Copolymers in particular based on styrene, on acrylic acid, and the like, are commonly resorted to in numerous uses, for example dispersion and grinding of pigments or latex stabilization. In latexes and paints in particular, it is important in addition for said copolymers to be soluble in alkaline media.
  • amphiphilic copolymers obtained by the “conventional” radical route generally have a relatively high polydispersity index (PI), as indicated, for example, in patent application EP 0 697 422.
  • PI polydispersity index
  • This patent application describes a method for the solution polymerization of a styrene (or substituted styrene) copolymer with a monomer having carboxyl functional groups and the use of the copolymers obtained in surface cleaning solutions.
  • These copolymers have number-average molar masses (Mn) of between 500 g/mol and 50 000 g/mol and high polydispersity indices (typically between 1.8 and 7.5).
  • Controlled radical polymerization based on a RAFT agent is already known, in particular from the publications of international applications WO 98/01478, WO 99/05099 and WO 99/31144, which recommend the use of certain sulfur-comprising molecules of the family of the dithioesters, dithiocarbonates, dithiocarbamates and trithiocarbonates as transfer agents in order to obtain (co)polymers having narrow polydispersity indices and describe the “reversible addition-fragmentation polymerization” polymerization process.
  • the block copolymers thus obtained have variable compositions (20 to 50 acrylic acid units and 10 to 50 n-butyl acrylate units) with a number-average molecular weight (Mn) of less than 9000 g/mol and are characterized by a polydispersity index of between 1.4 and 2.3.
  • Mn number-average molecular weight
  • the paper Macromolecules (2006), 39, 8632-8638, describes the synthesis of an acrylic acid/styrene gradient copolymer by controlled radical polymerization with a RAFT agent, said copolymer subsequently being used directly as seed for the emulsion synthesis of polystyrene or poly(n-butyl acrylate).
  • the gradient copolymer is obtained in several stages, one of which consists of an addition of water to the copolymer, obtained in the gel form, until spontaneous phase inversion occurs and a translucent solution is obtained.
  • the amount of water added is high since the level of solid disclosed is of the order of 12% by weight.
  • the initial gel and the translucent solution comprise a high residual amount of monomers (approximately 45% by weight in the gel).
  • An additional stage of conversion of the residual monomers at 60° C. for 12 hours is necessary in order to obtain a degree of conversion of 94% by weight. This process, in several stages carried out over a long period of time, is not appropriate either for use on the industrial scale.
  • one objective of the invention consists in providing a high-yield process for the synthesis of amphiphilic gradient copolymers which are soluble in alkaline media, which have a low polydispersity index and which have a high level of solid.
  • Another objective of the invention consists in providing a process for the synthesis of amphiphilic gradient copolymers which are soluble in alkaline media, which have a low polydispersity index and which have a high level of solid, said process being easily operated industrially and consuming little energy.
  • the present invention relates to a process for the preparation of an amphiphilic gradient copolymer by Controlled Radical Polymerization, in the presence of a RAFT (Reversible Addition Fragmentation Transfer) agent, comprising at least the following stages:
  • the hydrophilic monomer which can be polymerized by the radical route is chosen from the following monomers, which are spontaneously hydrophilic or which a simple conversion (quaternization of an amine or neutralization of an acid) renders hydrophilic in the polymer structure:
  • hydrophilic monomer is understood to mean, in the context of the invention, monomers which form water-soluble homopolymers.
  • hydrophobic monomers are generally chosen from the following monomers:
  • hydrophobic monomers is understood here to mean the monomers which form water-insoluble homopolymers.
  • water-soluble used here in connection with a polymer means that the polymer is soluble in water at 25° C. at a concentration by weight of at least 0.1%, preferably at least 1%, more preferably still of at least 5% and most preferably of at least 15%.
  • the mixture of the monomers to be polymerized, a radical polymerization initiator and a RAFT agent for controlling the polymerization are introduced into a stirred reactor optionally comprising at least one solvent.
  • the proportions of hydrophilic monomer(s) and of hydrophobic monomer(s) in the starting reaction medium can vary within wide limits and in general the amount of hydrophilic monomer(s) is between 5% and 95% by weight, with respect to the total weight of monomer(s), preferably between 15% and 85% and more preferably between 25% and 75%.
  • hydrophilic monomers chosen from acrylic acid, methacrylic acid, sodium styrenesulfonate and polyethylene glycol (meth)acrylates
  • hydrophobic monomers chosen from styrene, ⁇ -methylstyrene, n-butyl acrylate, ethyl acrylate and methyl methacrylate.
  • the proportion (acrylic acid+M i )/(styrene+M o ) is between 30/70 and 40/60 by weight.
  • the amount of M i can vary from 0 to 99.9% by weight, with respect to the sum of the hydrophilic monomers, and the amount of M o can vary from 0 to 99.9% by weight, with respect to the sum of the hydrophobic monomers.
  • the mixture of monomer(s) and more generally the reaction medium can be placed under an atmosphere of gas which is inert with regard to the radical polymerization, it being possible for said inert gas to be, for example, nitrogen or argon.
  • said inert gas can be, for example, nitrogen or argon.
  • the presence of inert gas is not, however, necessary.
  • the solvent of the reaction medium is preferably a solvent of the starting monomers and advantageously of the copolymer which would be formed. Mention may be made, among possible solvents, of water, linear or branched alcohols, glycols, such as diethylene glycol, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether, dimethyl sulfoxide, alkyl esters, in particular alkyl acetates, such as, inter alia, butyl acetate or ethyl acetate, ketones, such as methyl ethyl ketone (MEK) or methyl isobutyl ketone (MIBK), and the mixtures of two or more of them.
  • solvents of water, linear or branched alcohols, glycols, such as diethylene glycol, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether, dimethyl sulfoxide, alkyl esters, in particular alkyl acetates, such as, inter
  • the process of the invention can thus advantageously be carried out without the use of solvents which are regarded as harmful or toxic to the environment and/or the animal world and which are commonly used as indicated in the state of the art, such as dioxane, N-methylpyrrolidone, dimethylformamide, and others.
  • the process according to the invention is carried out in the absence of toxic and very toxic volatile organic compounds (VOCs) having in particular the following risk phrases: R33, R39, R40, R45, R46, R49 and R60 to R64.
  • VOCs toxic and very toxic volatile organic compounds
  • the polymerization initiator used in the process of the invention can be any type of radical polymerization initiator known to the person skilled in the art and chosen in particular but without implied limitation from initiators of azo, peroxide or redox type.
  • polymerization initiator is understood to mean conventionally a chemical entity capable of producing free radicals.
  • persulfates such as, for example, potassium persulfate, sodium persulfate and ammonium persulfate
  • metabisulfite salt for example sodium metabisulfite.
  • the polymerization initiator is added in an amount ranging from 1% to 50% by weight, with respect to the weight of RAFT transfer agent, preferably from 2% to 35% and more preferably still from 3% to 20%, for example approximately 5%.
  • the RAFT transfer agent employed in the process of the present invention can be of any type known to a person skilled in the art. Preference is given to the RAFT chain transfer agents corresponding to the following formula:
  • R is chosen from —CH 2 R 1 , —CHR 1 R′ 1 and —CR 1 R′ 1 R′′ 1 , with R 1 , R′ 1 and R′′ 1 , which are identical or different, each representing, independently of one another, a group chosen from optionally substituted alkyl, a saturated, unsaturated or aromatic carbocyclic or heterocyclic ring which is optionally substituted, optionally substituted alkylthio, optionally substituted alkoxy group, optionally substituted dialkylamino, organometallic group, acyl, acyloxy, carboxy (and its esters and/or salts), sulfonic acid (and its salts and/or sulfonates), alkoxy- or aryloxycarbonyl, and polymer chain prepared by any polymerization mechanism; where Z is chosen from hydrogen, halogen (chlorine, bromine, iodine), optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocycle, —SR 2
  • the R group as defined above can be released in the form of a radical R., which initiates the polymerization by free radicals.
  • chain transfer agents of dithioesters (compounds comprising at least one —C( ⁇ S)S— unit), dithiocarbonates or xanthates (compounds comprising at least one —O—C( ⁇ S)S— unit), dithiocarbamates (compounds comprising at least one —N—C( ⁇ S)S— unit) and trithiocarbonates (compounds comprising at least one —S—C( ⁇ S)S— unit).
  • dithioesters compounds comprising at least one —C( ⁇ S)S— unit
  • dithiocarbonates or xanthates compounds comprising at least one —O—C( ⁇ S)S— unit
  • dithiocarbamates compounds comprising at least one —N—C( ⁇ S)S— unit
  • trithiocarbonates compounds comprising at least one —S—C( ⁇ S)S— unit
  • Dithioesters which can advantageously be used in the context of the invention are those corresponding to the following formula (I):
  • Z represents a group chosen from —C 6 H 5 , —CH 3 , a pyrrole group, —OC 6 F 5 , a pyrrolidone group, —OC 6 H 5 , —OC 2 H 5 , —N(C 2 H 5 ) 2 and advantageously the —S—CH 2 —C 6 H 5 group (dibenzyl trithiocarbonate or DBTTC) of following formula (II):
  • DBTTC dibenzyl trithiocarbonate
  • the amounts of chain transfer agents employed generally range from 0.1% to 10% by weight, preferably from 0.1% to 5% by weight and particularly from 0.1% to 3% by weight, with respect to 100% by weight of monomer(s).
  • the reaction is carried out at a temperature of between 40° C. and 150° C., preferably between 50° C. and 140° C. and more preferably between 60° C. and 130° C.
  • the reaction can be carried out at atmospheric pressure or under slight pressure (such as, for example, at reflux of one or more of the compounds present in the reaction medium, in particular reflux of the solvent(s)).
  • the total amount of water added can vary within wide limits but, in general, it is preferable for the amount of water added to be such that the theoretical level of solid as amphiphilic copolymer formed at the end of the reaction is strictly greater than 40% by weight. Whether or not water has been added to the reaction medium, it is essential for the level of solid in the solution of amphiphilic copolymer obtained as final product to remain greater than 40% by weight.
  • aqueous solution having a pH of greater than 7, advantageously of between 8 and 10, for example an aqueous ammonia, sodium hydroxide or potassium hydroxide solution.
  • a basic aqueous solution is preferred in particular when one or more of the monomers comprise(s) acid functional groups, in particular carboxylic acid functional groups.
  • the reaction is continued, in the presence or in the absence of water, until a degree of conversion of the monomers of greater than 80%, preferably strictly of greater than 80%, more preferably of greater than 90% and entirely preferably of greater than 95%, in other words to obtain the highest possible degree of conversion for obvious reasons, both economic and of ease of industrial processing (low amount of recycling of the unconverted starting materials and small amounts of solvent(s) and the like).
  • the degree of conversion can be measured in the reaction medium by any means known per se, such as NMR, gas chromatography, gravimetry, after optional dilution, and others.
  • amphiphilic copolymer can be isolated according to conventional methods known to a person skilled in the art. It is possible to recover the unreacted monomers and the optional solvent and to recycle them, if desired.
  • the copolymer is obtained and recovered in the form of an aqueous dispersion and can be used as is.
  • the invention also applies to a process for the preparation of block copolymers, at least one of the blocks of which is a copolymer of the invention described above which has not been subjected to aftertreatment and the other block of which results from the polymerization of any type of monomer(s), chosen in particular from: alkyl (meth)acrylate, styrene and derivatives, functional (meth)acrylates with acid, anhydride, hydroxyl or amine functionality, poly(ethylene glycol) (polyethylene oxide), alone or as a mixture of two or more of them.
  • any type of monomer(s) chosen in particular from: alkyl (meth)acrylate, styrene and derivatives, functional (meth)acrylates with acid, anhydride, hydroxyl or amine functionality, poly(ethylene glycol) (polyethylene oxide), alone or as a mixture of two or more of them.
  • Said process is characterized by the use of at least one copolymer of the invention described above which has not been subjected to aftertreatment for the synthesis of a block copolymer, the other block(s) resulting from the polymerization of one or more of the monomers listed above.
  • the presence of the thiocarbonylthio groups in the copolymers is not desirable due to their reactivity toward various sources of radicals (temperature, UV radiation, atmospheric oxygen, moisture, and the like).
  • Such aftertreatments can also be envisaged when it is desired to improve the sulfurous odors of the amphiphilic copolymers directly obtained on conclusion of the reaction.
  • odor masking products or odorants can optionally be added during the copolymerization reaction, provided that they are inert with regard to said reaction.
  • one or more odor masking products or odorants can be added during the copolymerization reaction, or else after said reaction, or alternatively during and after said copolymerization reaction.
  • additives can, of course, be added to the amphiphilic copolymers obtained according to the process of the present invention and mention may be made, among these, without implied limitation, of pigments, antioxidants, stabilizers and others, and also their mixtures.
  • the process according to the present invention makes it possible to obtain amphiphilic copolymers at low temperature (typically of less than 150° C.), at atmospheric pressure or under slight excess pressure, according to different methods of synthesis (“bulk” (solvent-free) synthesis, synthesis in a solvent medium, synthesis in an aqueous medium or also synthesis in an aqueous/organic (solvent+water) medium).
  • amphiphilic copolymers thus obtained exhibit entirely advantageous characteristics and in particular being synthesized at high degrees of conversion and with controlled molar masses, while exhibiting low polydispersity indices.
  • the polydispersity index (PT) is defined by the Mw/Mn (weight-average molar mass/number-average molar mass) ratio, which is determined according to conventional methods known to a person skilled in the art and in particular by steric exclusion chromatography (SEC).
  • Mw/Mn weight-average molar mass/number-average molar mass ratio
  • amphiphilic copolymers obtained according to the process of the present invention thus exhibit low PI values, typically of between 1.2 and 2, generally between 1.2 and 1.8, more generally between 1.30 and 1.55.
  • the weight-average molar masses (Mw) of the amphiphilic copolymers of the process of the invention are generally between 1000 g/mol and 40 000 g/mol, preferably between 2000 g/mol and 30 000 g/mol and entirely preferably between 3000 g/mol and 20 000 g/mol.
  • amphiphilic copolymers obtained according to the process of the present invention exhibit lower viscosities, in particular in solution, than the commercially available amphiphilic copolymers obtained according to processes by the conventional radical route.
  • amphiphilic copolymers obtained according to the process of the present invention have uses in various fields of application, in particular as surfactants for stabilizing emulsions, or as dispersants for pigments and/or inorganic fillers, or also as agents for helping in the grinding of inorganic fillers, which are used in the preparation of formulations for paints, inks and other coating formulations.
  • amphiphilic copolymers Due to their low PI, the amphiphilic copolymers can be used in smaller amounts in comparison with the amounts used with similar copolymers exhibiting higher PI values.
  • the reaction medium is brought to 80° C. and this temperature is maintained by thermal regulation for a few minutes and then various stationary temperature phases make it possible to reach a value of 125° C. in the reactor at the end of the polymerization.
  • the molecular weights of the polymer as polystyrene (PS) equivalent, determined by SEC, are 9000 g/mol for the number-average molar mass (Mn) and 13 200 g/mol for the weight-average molar mass (Mw).
  • the polydispersity index is 1.47.
  • the molecular weights of the polymer as polystyrene (PS) equivalent, determined by SEC, are 8700 g/mol for the number-average molar mass (Mn) and 13 200 g/mol for the weight-average molar mass (Mw).
  • the polydispersity index is 1.51.
  • the molecular weights of the polymer as polystyrene (PS) equivalent, determined by SEC, are 7350 g/mol for the number-average molar mass (Mn) and 10 420 g/mol for the weight-average molar mass (Mw).
  • the polydispersity index is 1.42.
  • Example 4a is carried out according to the following data:
  • a 28% Normapur aqueous ammonia solution is diluted with distilled water until a pH of 12 is achieved.
  • the level of solid (SC) is 30%.
  • the combined mixture is vigorously stirred at ambient temperature until the polymer has completely dissolved, after which the pH is measured (using pH paper).
  • the viscosity is measured on a Brookfield type LVTCP viscometer, the temperature of which is regulated by a Haake D8 bath.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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  • Inks, Pencil-Leads, Or Crayons (AREA)
US13/058,383 2008-08-12 2009-08-11 Method for snythesizing amphiphilic gradient copolymers soluble in an alkaline medium Abandoned US20110136963A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FRFR08/55548 2008-08-12
FR0855548A FR2935000B1 (fr) 2008-08-12 2008-08-12 Procede de synthese de copolymeres amphiphiles a gradient de compositon et solubles en milieu alcalin
PCT/FR2009/051581 WO2010018344A1 (fr) 2008-08-12 2009-08-11 Procede de synthese de copolymeres amphiphiles a gradient et solubles en milieu alcalin

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EP (1) EP2313440B1 (fr)
JP (1) JP2011530640A (fr)
CN (1) CN102177183A (fr)
FR (1) FR2935000B1 (fr)
WO (1) WO2010018344A1 (fr)

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US8946360B2 (en) 2010-09-22 2015-02-03 Commonwealth Scientific And Industrial Research Organisation Continuous flow polymerisation process
WO2018141740A1 (fr) * 2017-01-31 2018-08-09 Archroma Ip Gmbh Copolymère, solution aqueuse comprenant le copolymère et procédé permettant de réduire les effets négatifs du brai naturel et des contaminants adhésifs dans les opérations de réduction en pâte et de fabrication de papier
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FR3013711B1 (fr) * 2013-11-26 2015-12-11 Coatex Sas Procede de polymerisation de l'acide (meth)acrylique en solution, solutions de polymeres obtenues et leurs utilisations
CN106008797A (zh) * 2016-07-04 2016-10-12 苏州大学 一种聚丙烯腈梯度共聚物及其可控合成方法
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CN109160973B (zh) * 2018-07-27 2021-01-12 天津安浩生物科技有限公司 一种马来酸酐/α-芳烯共聚物的水相超声合成方法
CN110437389B (zh) * 2019-07-08 2022-10-21 南京林业大学 一种阳离子丙烯酸酯改性环氧乳液的制备方法
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CN102177183A (zh) 2011-09-07
EP2313440A1 (fr) 2011-04-27
WO2010018344A1 (fr) 2010-02-18
EP2313440B1 (fr) 2013-07-17
FR2935000A1 (fr) 2010-02-19
FR2935000B1 (fr) 2011-07-01

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